936475-05-7Relevant academic research and scientific papers
Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: Development of the method and mechanistic investigations
Harris, Jason R.,Haynes, M. Taylor,Thomas, Andrew M.,Woerpel
supporting information; experimental part, p. 5083 - 5091 (2010/10/19)
(Figure presented) A method that allows for the reduction of protected hydroperoxides by employing catalytic amounts of phosphine is presented. The combination of a titanium(IV) alkoxide and a siloxane allowed for the chemoselective reduction of phosphine oxides in the presence of alkyl silyl peroxides. Subsequent reduction of the peroxide moiety by phosphine provided the corresponding silylated alcohols in useful yields. Mechanistic experiments, including crossover experiments, support a mechanism in which the peroxide group was reduced and the silyl group was transferred in a concerted step. Labeling studies with 17O-labeled peroxides demonstrate that the oxygen atom adjacent to the silicon atom is removed from the silyl peroxide.
Kinetic resolution of hydroperoxides with enantiopure phosphines: Preparation of enantioenriched tertiary hydroperoxides
Driver, Tom G.,Harris, Jason R.,Woerpel
, p. 3836 - 3837 (2008/02/13)
An efficient reductive kinetic resolution strategy capable of accessing optically active tertiary hydroperoxides is reported. Readily accessible tertiary hydroperoxides are resolved with commercially available (R)- or (S)-xylyl-PHANEPHOS with selectivity factors as large as 37. The resulting bis(phosphine oxide) can be recycled in high yields. The isolated mono(phosphine oxide) intermediate resolved hydroperoxides with the same selectivity as the parent bisphosphine. Copyright
